Recent experiments have shown that Ta@Si16+ is a very stable cation from which it should be possible to create Si-based cluster assembled materials. In this paper we have studied, by means of first-principles spin-dependent generalized gradient approximation calculations, the structural and electronic properties of the following systems: (i) Ta@Sin+ clusters in the range n = 14–18; (ii) (Ta@Si16F)m aggregates with sizes m = 1–8 formed by Ta@Si16F molecules; (iii) infinite wires formed by stacking triangular (Ta@Si16F)3 aggregates twisted 60◦ to each other along the vertical axis; and (iv) the fcc phase of bulk Ta@Si16F. The minimum-energy Ta@Si16+ cluster shows C3v symmetry, having 40 meV smaller total energy than a fullerenelike D4d isomer. However, the molecule Ta@Si16F formed with that D4d isomer is 40 meV more stable than that formed with the C3v one. We have optimized several [Ta@Si16F]n aggregates (n = 1–8) which contain the Ta@Si16 unit with D4d symmetry. The more bound (Ta@Si16F)6 aggregate is formed by stacking vertically two triangular (Ta@Si16F)3 aggregates which are twisted 60◦ to each other. The infinite wire formed with that (Ta@Si16F)6 aggregate as the unit cell has a cohesive energy 1.88 eV and a small highest occupied molecular orbital–lowest occupied molecular orbital gap. We have optimized also a metastable fcc bulk phase having the Ta@Si16F supermolecule as the unit cell. A Birch-Murnaghan fit to that phase produces a cohesive energy 0.84 eV at lattice constant 12.27 A, with bulk modulus 7.55 GPa and a phase stability to isotropic compression smaller than 0.75 GPa. That phase is nonmagnetic and shows a band gap of 0.20 eV. Using the values of hardness of Ta@Si16F molecules, we estimated a correction enhancement factor ∼3 to that small band gap. For that metastable solid we performed a 13.5-ps run of first-principles molecular dynamics annealing at 300 K and constant volume, and we found that the Ta@Si16F supermolecule in the fcc cell becomes severely distorted after the first 5 ps.